Preparation method of soldering flux and joint body

Abstract

The invention adopts a soldering flux containing rosin, terpene phenol resin and an activator. The hydroxyl value of the terpene phenol resin exceeds 130 mgKOH / g. The activator includes a halide salt of a primary amine.

Description

Technical Field

[0001] The present invention relates to a method for preparing a soldering flux and a joint body. This application claims priority based on Japanese Patent Application No. 2021-182146 filed in Japan on November 8, 2021, and the contents thereof are incorporated herein by reference. Background Art

[0002] Usually, fixing components to a substrate and electrically connecting components to the substrate are performed by soldering. In soldering, flux, solder, and solder paste mixed with flux and solder are used.

[0003] The flux has the ability to chemically remove the metal surface of the object to be soldered and the metal oxides present in the solder, and to allow the metal elements to move at the boundary between the two. Therefore, by soldering with the flux, an intermetallic compound is formed between the two, thereby obtaining a strong joint.

[0004] In soldering, a method such as reflow soldering or flow soldering is used depending on the size of the object to be joined.

[0005] In reflow soldering, solder paste is first printed on a substrate, then components are mounted, and the substrate with components mounted is heated in a heating furnace called a reflow oven to perform soldering.

[0006] In flow soldering, first, flux is applied to a substrate on which components are mounted, and then soldering is performed by bringing molten solder jetting from below into contact with the soldering surface while the substrate on which components are mounted is conveyed.

[0007] The flux used in soldering generally contains a resin component, a solvent, an activator, etc. For example, the embodiment of Patent Document 1 describes a flux for flow soldering, which contains rosin as a resin component and an organic acid, an organic halogen compound or an amine hydrohalide as an activator.

[0008] Prior art documents

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 6617848 Summary of the invention

[0011] Problems to be solved by the present invention

[0012] The resin component and activator contained in the flux remain as flux residue at the joint between the component and the substrate after soldering. Depending on the activator contained in the flux, it is sometimes easy to precipitate in the flux residue after soldering. The activator precipitated in the flux residue absorbs moisture in the air and ionizes. The ionized activator corrodes the metal and causes migration.

[0013] Therefore, an object of the present invention is to provide a flux and a method for producing a joint body that can further suppress the precipitation of an activating agent in the flux residue after soldering.

[0014] Means of solving the problem

[0015] The present invention includes the following aspects.

[0016] A first aspect of the present invention is a soldering flux comprising rosin, a terpene-phenol resin, and an activator, wherein the terpene-phenol resin has a hydroxyl value exceeding 130 mgKOH / g, and the activator comprises a halide salt of a primary amine.

[0017] In the soldering flux of the first aspect, the halide salt of the primary amine is preferably a compound represented by the following general formula (1).

[0018] R 1 -NH2·R 2 ···(1)

[0019] [Where R 1 represents a hydrocarbon group which may have a substituent. 2 represents HX, BX3 or HBX4. X represents a halogen atom.]

[0020] In the soldering flux of the first aspect, the content of the terpene phenol resin is preferably 0.1% by mass or more and 10% by mass or less relative to the total mass (100% by mass) of the soldering flux.

[0021] In the soldering flux of the first aspect, the content of the halide salt of the primary amine is preferably 0.01% by mass or more and 5% by mass or less relative to the total mass (100% by mass) of the soldering flux.

[0022] In the soldering flux of the first aspect, the ratio (mass ratio) of the content of the halide salt of the primary amine relative to the content (100 parts by mass) of the terpene-phenol resin is preferably 5 parts by mass or more and 150 parts by mass or less.

[0023] In the soldering flux of the first aspect, the soldering flux preferably further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

[0024] A second aspect of the present invention is a method for producing a bonded body, comprising the step of obtaining a bonded body by soldering a solder alloy on a surface of a substrate treated with the flux according to the first aspect.

[0025] Effects of the Invention

[0026] According to the present invention, it is possible to provide a flux and a method for producing a joint body that can further suppress the precipitation of an activating agent in the flux residue after soldering. DETAILED DESCRIPTION

[0027] (Flux)

[0028] The soldering flux of the first embodiment contains rosin, terpene phenol resin and an activator. The terpene phenol resin has a hydroxyl value exceeding 130 mgKOH / g. The activator contains a halide salt of a primary amine.

[0029] The flux of the first aspect can be used for either flow soldering or reflow soldering, but is preferably used for flow soldering.

[0030] The substrate used for flow soldering is made of a cheap and difficult-to-wet material and has the characteristic of being easily oxidized. In addition, the soldering time of flow soldering is short. For these reasons, a highly active activator is used in flow soldering. A highly active activator is difficult to dissolve in the flux residue containing resin etc. after soldering and will precipitate in the flux residue. In flow soldering, a halide salt of a primary amine is used as a highly active activator.

[0031] In the first aspect of the flux, a terpene phenol resin having a hydroxyl value exceeding 130 mgKOH / g is used for the halide salt of a primary amine as an activator. This allows the activator to be uniformly dissolved in the flux residue, thereby preventing it from precipitating in the flux residue.

[0032] In this specification, the solid content of the flux refers to all components remaining after removing only the solvent from the flux.

[0033] In the present specification, the hydroxyl value of the terpene phenol resin refers to the hydroxyl value measured by the potentiometric titration method according to 7.2 of JIS K0070 "Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products".

[0034] The hydroxyl value measured by this method is a weighted average value of the hydroxyl values ​​of all types of terpene phenol resins contained in the flux.

[0035] Hereinafter, an embodiment in which the flux of the first aspect is applied to a flux for flow soldering will be described.

[0036] The soldering flux of the above-mentioned embodiment contains rosin, terpene phenol resin, activator, solvent (S), and other components as needed.

[0037] <Rosin>

[0038] In the present invention, "rosin" includes natural resins containing abietic acid as a main component, mixtures of abietic acid and its isomers, and substances obtained by chemically modifying natural resins (sometimes referred to as rosin derivatives).

[0039] The total content of abietic acid and isomers of abietic acid in the natural resin is, for example, 40% by mass or more and 80% by mass or less relative to the natural resin.

[0040] In the present specification, the term "main component" refers to a component whose content in the compound is 40% by mass or more among the components constituting the compound.

[0041] Representative examples of isomers of abietic acid include neoabietic acid, palustric acid, and levopimaric acid. The structure of abietic acid is shown below.

[0042] [Chemical formula 1]

[0043]

[0044] Examples of the “natural resin” include gum rosin, wood rosin, and tall oil rosin.

[0045] In the present invention, "substances obtained by chemically modifying natural resins (rosin derivatives)" include substances obtained by subjecting the "natural resins" to one or more treatments selected from hydrogenation, dehydrogenation, neutralization, alkylene oxide addition, amidation, dimerization and polymerization, esterification, and Diels-Alder cycloaddition.

[0046] Examples of the rosin derivative include purified rosin and modified rosin.

[0047] Examples of the modified rosin include hydrogenated rosin, polymerized rosin, polymerized hydrogenated rosin, disproportionated rosin, acid-modified rosin, rosin ester, acid-modified hydrogenated rosin, acid-modified disproportionated rosin, acid-anhydride-modified disproportionated rosin, phenol-modified rosin and α,β-unsaturated carboxylic acid-modified products (acrylated rosin, maleated rosin, fumarated rosin, etc.), purified products, hydrogenated products and disproportionated products of the polymerized rosin, purified products, hydrogenated products and disproportionated products of the α,β-unsaturated carboxylic acid-modified products, abietol, abietamine, hydrogenated abietol, rosin ester, hydrogenated rosin ester, rosin soap, hydrogenated rosin soap, acid-modified rosin soap, and the like.

[0048] The rosin may be used alone or in combination of two or more.

[0049] As the rosin, a rosin derivative is preferably used.

[0050] As the rosin derivative, it is preferable to use one or more selected from the group consisting of acid-modified hydrogenated rosin, acid-modified rosin, hydrogenated rosin, polymerized rosin and rosin ester.

[0051] As the acid-modified hydrogenated rosin, acrylic acid-modified hydrogenated rosin is preferably used.

[0052] As the acid-modified rosin, acrylic acid-modified rosin is preferably used.

[0053] The content of the rosin in the flux is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 35% by mass or less, and further preferably 4.5% by mass or more and 20% by mass or less, relative to the total amount of the flux (100% by mass).

[0054] In the solid content of the flux, the content of the rosin is preferably 30% by mass or more and 95% by mass or less, more preferably 45% by mass or more and 95% by mass or less, and further preferably 50% by mass or more and 95% by mass or less, relative to the total amount (100% by mass) of the solid content.

[0055] <Terpene phenol resin>

[0056] In the present specification, the terpene-phenol resin refers to a copolymer of a terpene monomer and phenols, a hydrogenated product of the copolymer, and a copolymer of a terpene monomer, a monomer other than the terpene monomer, and phenols, and a hydrogenated product of the copolymer.

[0057] Examples of the terpene phenol resin include terpene resins, modified terpene resins, terpene phenol resins, and modified terpene phenol resins.

[0058] Examples of the modified terpene resin include hydrogenated terpene resin, aromatic modified terpene resin, hydrogenated aromatic modified terpene resin, and the like.

[0059] Examples of the modified terpene-phenol resin include hydrogenated terpene-phenol resins and the like.

[0060] Terpene monomers include, for example, hemiterpenes having 5 carbon atoms such as isoprene, monoterpenes having 10 carbon atoms, sesquiterpenes having 15 carbon atoms, diterpenes having 20 carbon atoms, diperpenes having 25 carbon atoms, triterpenes having 30 carbon atoms, and tetraterpenes having 40 carbon atoms.

[0061] Examples of the phenols include phenol, cresol, and xylenol.

[0062] The terpene phenol resin has a hydroxyl value exceeding 130 mgKOH / g, preferably 140 mgKOH / g or more, more preferably 150 mgKOH / g or more, further preferably 160 mgKOH / g or more, particularly preferably 170 mgKOH / g or more, and most preferably 180 mgKOH / g or more.

[0063] The upper limit of the hydroxyl value of the terpene phenol resin is not particularly limited as long as the effects of the present invention can be exhibited, and may be, for example, 300 mgKOH / g or less, 250 mgKOH / g or less, or 230 mgKOH / g or less.

[0064] For example, the hydroxyl value of the terpene-phenol resin may be greater than 130 mgKOH / g and less than 300 mgKOH / g, preferably greater than 140 mgKOH / g and less than 300 mgKOH / g, more preferably greater than 150 mgKOH / g and less than 300 mgKOH / g, further preferably greater than 160 mgKOH / g and less than 300 mgKOH / g, particularly preferably greater than 170 mgKOH / g and less than 300 mgKOH / g, and most preferably greater than 180 mgKOH / g and less than 300 mgKOH / g.

[0065] Alternatively, the hydroxyl value of the terpene-phenol resin may be greater than 130 mgKOH / g and less than 250 mgKOH / g, preferably greater than 140 mgKOH / g and less than 250 mgKOH / g, more preferably greater than 150 mgKOH / g and less than 250 mgKOH / g, further preferably greater than 160 mgKOH / g and less than 250 mgKOH / g, particularly preferably greater than 170 mgKOH / g and less than 250 mgKOH / g, and most preferably greater than 180 mgKOH / g and less than 250 mgKOH / g.

[0066] When the hydroxyl value of the terpene phenol resin exceeds the above lower limit, the halide salt of the highly active primary amine is uniformly dissolved in the flux residue, thereby further improving the effect of suppressing its precipitation in the flux residue.

[0067] When the hydroxyl value of the terpene phenol resin is equal to or less than the upper limit, the moisture absorption of the flux residue can be further reduced, thereby further suppressing the reduction in the insulation resistance value of the flux and further suppressing the occurrence of migration.

[0068] Examples of the terpene phenol resin include easily available resins such as YS Polyster (terpene phenol resin: manufactured by Yasuhara Chemical Co., Ltd.), TAMANOL (terpene phenol resin: manufactured by Arakawa Chemical Industries, Ltd.), TELLTAG 80 (terpene phenol resin: manufactured by Nippon Terpene Chemical Co., Ltd.), and Sylvares TP (terpene phenol resin: manufactured by Air Brown Co., Ltd.) A terpene phenol resin can be selected from these resins so as to obtain a desired hydroxyl value.

[0069] The terpene phenol resins may be used alone or in combination of two or more.

[0070] The soldering flux of this embodiment may contain one type of terpene-phenol resin having a hydroxyl value exceeding 130 mgKOH / g. Alternatively, the soldering flux of this embodiment may contain a resin having a hydroxyl value exceeding 130 mgKOH / g obtained by weighted averaging of two or more terpene-phenol resins having different hydroxyl values ​​or structures.

[0071] The content of the terpene phenol resin in the soldering flux is preferably 0.1% to 10% by mass, more preferably 0.2% to 5% by mass, and further preferably 0.5% to 4% by mass, relative to the total amount of the soldering flux (100% by mass).

[0072] In the solid content of the flux, the content of the terpene phenol resin is preferably 3 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 40 mass % or less, and further preferably 5 mass % or more and 35 mass % or less, relative to the total amount of the solid content (100 mass %).

[0073] When the content of the terpene-phenol resin is equal to or greater than the above lower limit, precipitation of the activator in the flux residue after soldering can be further suppressed.

[0074] When the content of the terpene phenol resin is equal to or less than the above upper limit, the possibility that the viscosity of the flux becomes too high can be reduced.

[0075] The mixing ratio of rosin and terpene-phenol resin, measured as a mass ratio of rosin / terpene-phenol resin, that is, the ratio (mass ratio) of the rosin content to the terpene-phenol resin content, is preferably 0.5 or more and 20 or less, more preferably 1 or more and 16 or less, and further preferably 2 or more and 16 or less.

[0076] <Activator>

[0077] 《Special active agent》

[0078] The soldering flux of the present embodiment contains a halide salt of a primary amine as a specific activator.

[0079] Examples of the halide salt of the primary amine include hydrohalide salts, tetrafluoroborate salts, trifluoroborate salts and the like.

[0080] The halide salt of the primary amine is preferably a hydrohalide salt or a tetrafluoroborate salt.

[0081] As the substituent which the primary amine has (that is, R in R—NH 2 ), for example, there can be mentioned a hydrocarbon group which may have a substituent.

[0082] The hydrocarbon group which may have a substituent may be linear, branched or cyclic.

[0083] The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

[0084] When the hydrocarbon group which may have a substituent is a linear or branched hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4.

[0085] When the hydrocarbon group is a straight chain or branched chain, examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl and neohexyl.

[0086] When the hydrocarbon group which may have a substituent is a cyclic hydrocarbon group, the number of carbon atoms in the hydrocarbon group is preferably 3 to 20, more preferably 4 to 12, and even more preferably 4 to 8.

[0087] When the hydrocarbon group is cyclic, examples of the hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cycloundecyl.

[0088] Examples of the substituent that the hydrocarbon group may have include a halogen atom, a hydroxyl group, and a carboxyl group.

[0089] The halide salt of the primary amine may be used alone or in combination of two or more.

[0090] Examples of the primary amine include ethylamine and cyclohexylamine.

[0091] [Compound represented by general formula (1)]

[0092] The halide salt of the primary amine is preferably a compound represented by the following general formula (1).

[0093] R 1 -NH2·R 2 ···(1)

[0094] [Where R1 represents a hydrocarbon group which may have a substituent. 2 represents HX, BX3 or HBX4. X represents a halogen atom.]

[0095] In the general formula (1), R 1 The hydrocarbon group may include the hydrocarbon groups mentioned above in the substituent (R) possessed by the primary amine.

[0096] R 2 represents HX, BX3 or HBX4. X represents a halogen atom.

[0097] Examples of X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0098] BX3 is preferably boron trifluoride (BF3).

[0099] HBX4 is preferably tetrafluoroboric acid (HBF4).

[0100] R 2 HX is preferred.

[0101] Examples of the compound represented by the general formula (1) include ethylamine hydrofluoride, ethylamine hydrochloride, ethylamine hydrobromide, and cyclohexylamine tetrafluoroborate.

[0102] The specific active agent may be used alone or in combination of two or more.

[0103] The content of the halide salt of the primary amine in the flux is preferably 0.01% by mass to 5% by mass, more preferably 0.1% by mass to 2% by mass, and further preferably 0.15% by mass to 1.5% by mass, relative to the total mass of the flux (100% by mass).

[0104] In the solid content of the flux, the content of the halide salt of the primary amine is preferably 0.2% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and further preferably 1% by mass or more and 10% by mass or less, relative to the total amount of the solid content (100% by mass).

[0105] When the content of the halide salt of the primary amine is equal to or greater than the lower limit, the wettability of the flux can be further improved.

[0106] When the content of the halide salt of the primary amine is equal to or less than the upper limit, the precipitation of the activator in the flux residue after soldering can be further suppressed.

[0107] The mixing ratio of the halide salt of the primary amine and the terpene-phenol resin, measured as the mass ratio represented by the halide salt of the primary amine / terpene-phenol resin, that is, the ratio of the halide salt of the primary amine to the content (100 parts by mass) of the terpene-phenol resin, is preferably 5 parts by mass or more and 150 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less, further preferably 5 parts by mass or more and less than 100 parts by mass, and most preferably 5 parts by mass or more and 50 parts by mass or less.

[0108] When the ratio of the content of the halogenated salt of the primary amine is equal to or greater than the lower limit, weldability can be improved.

[0109] When the ratio of the content of the halide salt of the primary amine is equal to or less than the upper limit, the precipitation of the activator in the flux residue after soldering can be further suppressed.

[0110] Other active agents

[0111] The activator contained in the soldering flux of the present embodiment may contain other activators in addition to the above-mentioned specific activators.

[0112] Examples of other activators include halogen-based activators other than the above-mentioned halogenated salts of primary amines, organic acid-based activators, and amine-based activators.

[0113] [Other halogen-based activators]

[0114] Examples of other halogen-based activators include amine halide salts other than those mentioned above (other amine halide salts), and organic halogen compounds other than amine halide salts.

[0115] Other amine halides:

[0116] As other amine halide salts, for example, hydrohalide salts, tetrafluoroborate salts and trifluoroborate salts can be mentioned.

[0117] Examples of the hydrogen halide include hydrides of chlorine, bromine and iodine.

[0118] Examples of the amine in the amine halide salt include alkylamine compounds other than the above-mentioned primary amines, azoles, guanidines, amino alcohol compounds, rosin amine, and the like.

[0119] Examples of the alkylamine compound include ethylenediamine, triethylenetetramine, hexadecylamine, and stearylamine.

[0120] Examples of the azoles include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2″-methylimidazolyl-(1′)]-ethyl tris-imidazolyl 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 2-methylimidazoline, 2-phenylimidazoline, 2,4-diamino-6-vinyl-s-triazine, 2 ,4-diamino-4,6-vinyl-s-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-s-triazine, epoxy-imidazole adduct, 2-methylbenzimidazole, 2-octylbenzimidazole, 2-pentylbenzimidazole, 2-(1-ethylpentyl)benzimidazole, 2-nonylbenzimidazole, 2-(4-thiazolyl)benzimidazole, benzimidazole, 1,2,4-triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2 ,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol], 6-(2-benzotriazolyl)-4-tert-octyl-6'-tert-butyl-4'-methyl-2,2'-methylenebisphenol, 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, carboxybenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]methylbenzotriazole, 2,2'-[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-(2,3-dicarboxypropyl)benzotriazole, 1-[(2-ethylhexylamino)methyl]benzotriazole, 2,6-Bis[(1H-benzotriazol-1-yl]methyl]-4-methylphenol, 5-methylbenzotriazole, 5-phenyltetrazolyl, etc.

[0121] Examples of the guanidines include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylguanidine, 1,3-di-o-isopropylphenylguanidine, and 1,3-di-o-isopropylphenyl-2-propionylguanidine.

[0122] Examples of the amino alcohol compound include N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and the like.

[0123] Examples of the rosin amine include dehydrorosin ethylamine and dihydrorosin ethylamine.

[0124] Rosin amine refers to so-called disproportionated rosin amine.

[0125] The structures of dehydroabietin ethylamine and dihydroabietin ethylamine are shown below.

[0126] [Chemical formula 2]

[0127]

[0128] More specifically, examples of the amine hydrohalide salt include hexadecylamine hydrobromide, stearylamine hydrobromide, diphenylguanidine hydrobromide, stearylamine hydrochloride, diethylaniline hydrochloride, diethanolamine hydrochloride, pyridine hydrobromide, diethylamine hydrobromide, dimethylamine hydrobromide, dimethylamine hydrochloride, rosinamine hydrobromide, 2-piperidine hydrobromide, 1,3-diphenylguanidine hydrochloride, dimethylbenzylamine hydrochloride, hydrazine hydrate hydrobromide, trinonylamine hydrobromide, diethylaniline hydrobromide, 2-diethylaminoethanol hydrobromide, 2-diethylaminoethanol hydrochloride, ammonium chloride, diallylamine hydrochloride, and diolefin hydrobromide. Propylamine hydrobromide, diethylamine hydrochloride, triethylamine hydrobromide, triethylamine hydrochloride, hydrazine hydrochloride, hydrazine dihydrochloride, hydrazine hydrobromide, hydrazine dihydrobromide, pyridine hydrochloride, aniline hydrobromide, n-octylamine hydrochloride, dodecylamine hydrochloride, ethylenediamine dihydrobromide, rosinamine hydrobromide, 2-phenylimidazole hydrobromide, 4-benzylpyridine hydrobromide, L-glutamic acid hydrochloride, N-methylmorpholine hydrochloride, betaine hydrochloride, 2-piperidine hydroiodide, 1,3-diphenylguanidine hydrofluoride, diethylamine hydrofluoride, rosinamine hydrofluoride, dicyclohexylamine tetrafluoroborate, boron trifluoride piperidine, etc.

[0129] Organohalogen compounds:

[0130] Examples of the organic halogen compound other than the amine hydrohalide salt include halogenated aliphatic compounds. The halogenated aliphatic hydrocarbon group refers to a group in which a part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group are substituted with halogen atoms.

[0131] Examples of the halogenated aliphatic compound include halogenated aliphatic alcohols and halogenated heterocyclic compounds.

[0132] Examples of the halogenated aliphatic alcohol include 1-bromo-2-propanol, 3-bromo-1-propanol, 3-bromo-1,2-propanediol, 1-bromo-2-butanol, 1,3-dibromo-2-propanol, 2,3-dibromo-1-propanol, 1,4-dibromo-2-butanol, and trans-2,3-dibromo-2-butene-1,4-diol.

[0133] Examples of the halogenated heterocyclic compound include compounds represented by the following general formula (3).

[0134] R 11 -(R 12 )n (3)

[0135] [Where R 11 represents an n-valent heterocyclic group. 12 represents a halogenated aliphatic hydrocarbon group.]

[0136] As R 11 The heterocyclic ring of the n-valent heterocyclic group in the formula (I) may be a ring structure in which a portion of the carbon atoms constituting the aliphatic hydrocarbon or aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the heterocyclic ring include an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The heterocyclic ring is preferably a 3- to 10-membered ring, and more preferably a 5- to 7-membered ring. Examples of the heterocyclic ring include an isocyanurate ring and the like.

[0137] R 12 The halogenated aliphatic hydrocarbon group in preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 3 to 5 carbon atoms. 12 Preferred are brominated aliphatic hydrocarbon groups and chlorinated aliphatic hydrocarbon groups, more preferred are brominated aliphatic hydrocarbon groups, and still more preferred are brominated saturated aliphatic hydrocarbon groups.

[0138] Examples of the halogenated heterocyclic compound include tris-(2,3-dibromopropyl)isocyanurate and the like.

[0139] In addition, as organic halogen compounds other than amine hydrohalides, for example, iodinated carboxyl compounds such as 2-iodobenzoic acid, 3-iodobenzoic acid, 2-iodopropionic acid, 5-iodosalicylic acid, and 5-iodoanthranilic acid; chlorinated carboxyl compounds such as 2-chlorobenzoic acid and 3-chloropropionic acid; halogenated carboxyl compounds such as brominated carboxyl compounds such as 2,3-dibromopropionic acid, 2,3-dibromosuccinic acid, and 2-bromobenzoic acid, hydrobromic acid, carbon tetrabromide, fatty acid methyl ester chloride (chlorinated paraffin), tetrabromoethane, etc.

[0140] The other halogen-based activators may be used alone or in combination of two or more.

[0141] [Organic acid surfactant]

[0142] Examples of the organic acid-based activator include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, citric acid, glycolic acid, salicylic acid, diglycolic acid, pyridinedicarboxylic acid, dibutylanilinodiglycolic acid, thioglycolic acid, dithioglycolic acid, terephthalic acid, p-hydroxyphenylacetic acid, picolinic acid, phenylsuccinic acid, phthalic acid, fumaric acid, maleic acid, lauric acid, benzoic acid, tartaric acid, Acid, tris(2-carboxyethyl)isocyanurate, glycine, 1,3-cyclohexanedicarboxylic acid, 2,2-di(hydroxymethyl)propionic acid, 2,2-di(hydroxymethyl)butyric acid, 2,3-dihydroxybenzoic acid, 2,4-diethylglutaric acid, 2-quinolinecarboxylic acid, 3-hydroxybenzoic acid, 4-tert-butylbenzoic acid, propionic acid, malic acid, p-anisic acid, stearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid, linolenic acid, palmitic acid, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester, dimer acid, trimer acid, hydrogenated dimer acid which is a hydrogenated product of dimer acid, hydrogenated trimer acid which is a hydrogenated product of trimer acid, and the like.

[0143] Examples of the dimer acid and trimer acid include a dimer acid as a reaction product of oleic acid and linoleic acid, a trimer acid as a reaction product of oleic acid and linoleic acid, a dimer acid as a reaction product of acrylic acid, a trimer acid as a reaction product of acrylic acid, a dimer acid as a reaction product of methacrylic acid, a trimer acid as a reaction product of methacrylic acid, a dimer acid as a reaction product of acrylic acid and methacrylic acid, a trimer acid as a reaction product of acrylic acid and methacrylic acid, a dimer acid as a reaction product of oleic acid, a trimer acid as a reaction product of oleic acid, a dimer acid as a reaction product of linoleic acid, a trimer acid as a reaction product of linolenic acid, a dimer acid as a reaction product of linolenic acid, a trimer acid as a reaction product of linolenic acid, a dimer acid as a reaction product of acrylic acid and oleic acid, a trimer acid as a reaction product of acrylic acid and linoleic acid, and a dimer acid as a reaction product of acrylic acid and oleic acid. Acid, trimer acid which is a reaction product of acrylic acid and linoleic acid, dimer acid which is a reaction product of acrylic acid and linolenic acid, trimer acid which is a reaction product of acrylic acid and linolenic acid, dimer acid which is a reaction product of methacrylic acid and oleic acid, trimer acid which is a reaction product of methacrylic acid and oleic acid, dimer acid which is a reaction product of methacrylic acid and linoleic acid, trimer acid which is a reaction product of methacrylic acid and linoleic acid, dimer acid which is a reaction product of methacrylic acid and linoleic acid, trimer acid which is a reaction product of methacrylic acid and linolenic acid, dimer acid which is a reaction product of oleic acid and linolenic acid, trimer acid which is a reaction product of linoleic acid and linolenic acid, dimer acid which is a reaction product of linoleic acid and linolenic acid, trimer acid which is a reaction product of linoleic acid and linolenic acid, hydrogenated dimer acid which is a hydrogenated product of the above dimer acids, hydrogenated trimer acid which is a hydrogenated product of the above trimer acids, and the like.

[0144] For example, the dimer acid, which is a reaction product of oleic acid and linoleic acid, is a dimer having 36 carbon atoms. Also, the trimer acid, which is a reaction product of oleic acid and linoleic acid, is a trimer having 54 carbon atoms.

[0145] The organic acid-based activators may be used alone or in combination of two or more.

[0146] From the viewpoint of further improving the wettability of the substrate, the flux of this embodiment preferably contains a highly polar organic acid as a highly active activator in addition to the above-mentioned primary amine halide salt. As the highly polar organic acid, for example, an organic acid having a solubility parameter (SP value) of 11 or more can be cited.

[0147] In this specification, the solubility parameter (SP value) refers to a value calculated from the molecular structure based on the Fedors method. The SP value (δ) can be obtained from the following formula (SP).

[0148] δ=(ΔE / ΔV) 1 / 2 (cal / cm 3 ) 1 / 2···(sp)

[0149] In the formula (sp), ΔE represents the total of the vaporization energies (cal / mol) of atoms and atomic groups in the molecule of the organic acid (A1).

[0150] ΔV represents the molar volume (cm2) of the atoms and atomic groups in the molecule of the organic acid (A1) at 25°C. 3 / mol).

[0151] As the evaporation energy and the molar volume, the values ​​described in Robert F. Fedors, A method for estimating both the solubility parameters and molar volumes of liquids. Polymer Engineering and Science, 14, 147-154 (1974) can be used.

[0152] Examples of organic acids having a solubility parameter (SP value) of 11 or more include oxalic acid (15.22), malonic acid (14.03), succinic acid (13.21), glutaric acid (12.61), adipic acid (12.15), pimelic acid (11.79), suberic acid (11.49), azelaic acid (11.25), sebacic acid (11.04), 2,4-diethylglutaric acid (14.89), 1,3-cyclohexanedicarboxylic acid (12.80), picolinic acid (12.78), 2,2-bis(hydroxymethyl)propionic acid (16.12), and 2,2-bis(hydroxymethyl)butanoic acid (19.07). The numerical values ​​in parentheses represent the SP values ​​of the organic acids.

[0153] Even if the flux of the present embodiment contains a highly polar organic acid in addition to the halide salt of the primary amine, the precipitation of the activator in the flux residue after soldering can be further suppressed.

[0154] The content of the organic acid activator in the flux is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 4% by mass, and further preferably 0.1% by mass to 3% by mass, relative to the total mass of the flux (100% by mass).

[0155] [Amine surfactant]

[0156] Examples of the amine-based activator include the amines exemplified as raw materials for the halogen-based activator in "Halogen-based activator".

[0157] The amine-based activator may be, for example, ethylamine, triethylamine, or cyclohexylamine.

[0158] The amine-based activators may be used alone or in combination of two or more.

[0159] <Solvent (S)>

[0160] Examples of the solvent (S) include water, alcohol solvents, glycol ether solvents, and terpineols.

[0161] Examples of the alcohol solvent include ethanol, 1-propanol, 2-propanol (isopropanol), 1,2-butanediol, isobornylcyclohexanol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,3-dimethyl-2,3-butanediol, 2-methylpentane-2,4-diol, 1,2-dimethyl-2,3-butanediol, 2-methyl-2,5-pentane-3-ol, 2,2-dimethyl-2,3-butanediol, 2-methyl-2,5-pentane-2,5-diol, 2,3-dimethyl-2,3-butanediol, 2-methyl-2,5-pentane-3-ol, 2,3-dimethyl-2,3-butane-2,3-ol, 2-methyl-2,5-pentane-2,5-di ... 1,1-tri(hydroxymethyl)propane, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 2,2'-oxybis(methylene)bis(2-ethyl-1,3-propanediol), 2,2-bis(hydroxymethyl)-1,3-propanediol, 1,2,6-trihydroxyhexane, 1-ethynyl-1-cyclohexanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, etc.

[0162] Examples of the glycol ether solvent include diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethylene glycol monohexyl ether (hexyl diglycol), diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, methpropylene triethylene glycol, butylpropylene triethylene glycol, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether.

[0163] The solvent (S) may be used alone or in combination of two or more.

[0164] From the viewpoint of improving volatility during preheating, the solvent (S) preferably contains a solvent (S1) having a boiling point of 100° C. or less. The boiling point of the solvent (S1) is preferably 60° C. or more and 100° C. or less, more preferably 70° C. or more and 100° C. or less, further preferably 75° C. or more and 100° C. or less, and particularly preferably 80° C. or more and 100° C. or less.

[0165] The content of the solvent (S1) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less, and may be 100% by mass, relative to the total mass (100% by mass) of the solvent (S). When the content of the solvent (S1) is above the lower limit, the volatility of the solvent (S) under preheating is easily increased.

[0166] From the viewpoint of solubility of the specific active agent, the solvent (S1) having a boiling point of 100° C. or less is preferably an alcohol solvent.

[0167] From the viewpoint of industrial low cost, the alcohol solvent preferably contains 2-propanol (isopropanol).

[0168] The content of the solvent (S) in the flux is preferably 40% by mass or more and 98% by mass or less, more preferably 60% by mass or more and 98% by mass or less, and further preferably 70% by mass or more and 98% by mass or less, relative to the total amount of the flux (100% by mass).

[0169] <Other ingredients>

[0170] The soldering flux of the present embodiment may contain other components in addition to the rosin, terpene phenol resin, activator, and solvent as necessary.

[0171] Examples of other components include a thixotropic agent, a resin component other than rosin and terpene phenol resin, a metal deactivator, a surfactant, a silane coupling agent, an antioxidant, and a colorant.

[0172] 《Resin components other than rosin and terpene-phenol resins (other resin components)》

[0173] Examples of other resin components include styrene resins, modified styrene resins, xylene resins, modified xylene resins, acrylic resins, polyethylene resins, acrylic-polyethylene copolymer resins, epoxy resins, and silicone resins.

[0174] Examples of the modified styrene resin include styrene acrylic resin, styrene maleic resin, etc. Examples of the modified xylene resin include phenol-modified xylene resin, alkylphenol-modified xylene resin, phenol-modified resol-type xylene resin, polyol-modified xylene resin, and polyoxyethylene-added xylene resin.

[0175] 《Metal passivator》

[0176] Examples of the metal deactivator include hindered phenol compounds and nitrogen compounds.

[0177] The "metal deactivator" mentioned here refers to a compound having the ability to prevent metal from deteriorating due to contact with a certain compound.

[0178] Hindered phenol compounds refer to phenol compounds having a bulky substituent (for example, a branched or cyclic alkyl group such as a tert-butyl group) at at least one ortho position of phenol.

[0179] The hindered phenol compound is not particularly limited, and examples thereof include bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)], N,N'-hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2,2'-methylenebis(6-tert-butyl-p-cresol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediolbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octyl)-1,4-diol 2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexamethylenebis( 3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxalamide, compounds represented by the following chemical formulas, etc.

[0180] [Chemical formula 3]

[0181]

[0182] (wherein, Z is an alkylene group which may be substituted. 101 and R 102 Each is independently an alkyl group, an aralkyl group, an aryl group, a heteroaryl group, a cycloalkyl group or a heterocycloalkyl group which may be substituted. 103 and R 104 Each is independently an alkyl group which may be substituted.)

[0183] Examples of the nitrogen compound in the metal deactivator include hydrazide nitrogen compounds, amide nitrogen compounds, triazole nitrogen compounds, and melamine nitrogen compounds.

[0184] As the hydrazide-based nitrogen compound, any nitrogen compound having a hydrazide skeleton may be used, and examples thereof include dodecanedioic acid bis[N2-(2-hydroxybenzoyl)hydrazide], N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazide, decanedicarboxylic acid disalicylic hydrazide, N-salicylic-N'-salicylic hydrazide, m-nitrophenyl hydrazide, 3-aminophthalhydrazide, phthalic acid dihydrazide, adipic acid hydrazide, oxalyl di(2-hydroxy-5-octylbenzylidene hydrazide), N'-benzoylpyrrolidonecarboxylic acid hydrazide, and N,N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hydrazide.

[0185] The amide nitrogen compound may be any nitrogen compound having an amide skeleton, and examples thereof include N,N′-bis{2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl}oxalamide.

[0186] The triazole nitrogen compound may be any nitrogen compound having a triazole skeleton, and examples thereof include N-(2H-1,2,4-triazol-5-yl)salicylamide, 3-amino-1,2,4-triazole, and 3-(N-salicyloyl)amino-1,2,4-triazole.

[0187] As the melamine-based nitrogen compound, any nitrogen compound having a melamine skeleton may be used, and examples thereof include melamine, melamine derivatives, etc. More specifically, examples thereof include triaminotriazine, alkylated triaminotriazine, alkoxyalkylated triaminotriazine, melamine, alkylated melamine, alkoxyalkylated melamine, N2-butylmelamine, N2,N2-diethylmelamine, N,N,N',N',N",N"-hexa(methoxymethyl)melamine, etc.

[0188] The metal deactivator preferably contains bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid][ethylenebis(oxyethylene)].

[0189] The content of the metal deactivator is preferably 0 mass % or more and 10.0 mass % or less, and more preferably 0.6 mass % or more and 3.0 mass % or less, relative to the total amount (100 mass %) of the soldering flux.

[0190] Surfactants

[0191] Examples of the surfactant include nonionic surfactants and weakly cationic surfactants.

[0192] Examples of the nonionic surfactant include polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers, aliphatic alcohol polyoxyethylene adducts, aromatic alcohol polyoxyethylene adducts, and polyhydric alcohol polyoxyethylene adducts.

[0193] Examples of the weak cationic surfactant include terminal diamine polyethylene glycol, terminal diamine polyethylene glycol-polypropylene glycol copolymer, aliphatic amine polyoxyethylene adducts, aromatic amine polyoxyethylene adducts, and polyamine polyoxyethylene adducts.

[0194] Examples of surfactants other than those described above include polyoxyalkylene acetylene glycols, polyoxyalkylene glycerol ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene esters, polyoxyalkylene alkylamines, and polyoxyalkylene alkylamides.

[0195] The soldering flux of one embodiment described above contains rosin, terpene phenol resin, a halide salt of a primary amine as a specific activator, and a solvent, and is suitable for flow soldering.

[0196] The specific activator is highly active and easily precipitates in the flux residue. However, even if the flux of this embodiment contains a halide salt of a primary amine, by containing a terpene phenol resin having a hydroxyl value exceeding 130 mgKOH / g in addition to rosin, precipitation of the activator in the flux residue after soldering can be further suppressed.

[0197] Although the reason for obtaining such an effect is not clear, it is presumed that the activator is uniformly dissolved and sealed in the flux residue containing rosin and terpene phenol resin after soldering by using the flux of the present embodiment.

[0198] (Method for preparing a conjugate)

[0199] The method for producing a bonded body according to the second aspect includes the step of obtaining a bonded body by soldering a solder alloy on the surface of a substrate treated with the flux according to the first aspect.

[0200] Hereinafter, one embodiment of the method for producing a joined body according to the second aspect will be described.

[0201] The method for producing a bonded body according to the present embodiment is a method that includes a component mounting step, a flux coating step, a preheating step, and a soldering step in sequence.

[0202] In the component mounting step, components are mounted on the substrate.

[0203] Examples of the substrate include a printed wiring board and the like.

[0204] Examples of the components include integrated circuits, transistors, diodes, resistors, capacitors, and the like.

[0205] In the flux application step, the flux of the above-described embodiment is applied to the soldering surface of the substrate on which components are mounted.

[0206] As the flux coating apparatus, there can be mentioned a spray flux coater, a foaming flux coater, etc. Among them, a spray flux coater is preferred from the viewpoint of the stability of the coating amount.

[0207] From the viewpoint of solderability, the amount of flux applied is preferably 30 to 180 mL / m 2 , more preferably 40 to 150 mL / m 2 , particularly preferably 50 to 120 mL / m 2 .

[0208] In the preheating step, the substrate on which the components are mounted is preheated. The temperature of the heated substrate in the preheating step is preferably 80 to 130°C, and more preferably 90 to 120°C.

[0209] In the soldering process, the soldering surface of the substrate on which the components are mounted is brought into contact with molten solder formed by melting a solder alloy.

[0210] The method of bringing the molten solder into contact with the soldering surface is not particularly limited as long as it is a method that can bring the molten solder into contact with the substrate. Examples of such a method include a jet method and a dipping method.

[0211] The jet method is a method of bringing the soldering surface of a substrate on which components are mounted into contact with a jet of molten solder. The immersion method is a method of bringing the soldering surface of a substrate on which components are mounted into contact with a stationary liquid surface of molten solder.

[0212] As the solder alloy, a solder alloy having a known composition can be used.

[0213] The solder alloy can also be a solder of Sn alone, or a solder alloy of Sn-Ag, Sn-Cu, Sn-Ag-Cu, Sn-Bi, Sn-In, etc., or a solder alloy to which Sb, Bi, In, Cu, Zn, As, Ag, Cd, Fe, Ni, Co, Au, Ge, P, etc. are added.

[0214] The solder alloy may be a Sn-Pb based solder alloy or a Sn-Pb based solder alloy to which Sb, Bi, In, Cu, Zn, As, Ag, Cd, Fe, Ni, Co, Au, Ge, P, etc. are added.

[0215] The solder alloy is preferably a Pb-free solder.

[0216] The soldering conditions in the soldering step may be appropriately set according to the melting point of the solder. For example, when a Sn-Ag-Cu solder alloy is used, the temperature of the molten solder is preferably 230 to 280°C, more preferably 250 to 270°C.

[0217] According to the method for producing a bonded body of the present embodiment described above, the precipitation of the activator in the flux residue on the obtained bonded body can be further suppressed, thereby reducing the possibility of migration in the obtained bonded body.

[0218] Other implementations:

[0219] The flux of the above-mentioned one embodiment is suitable for flow soldering, but the flux of the first embodiment is not limited thereto, and can also be used for reflow soldering.

[0220] Example

[0221] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples.

[0222] <Preparation of mixed solution>

[0223] (Test Examples 1 to 30)

[0224] Mixed solutions of the test examples were prepared with the compositions shown in Tables 1 to 6. In Tables 1 to 6, the numerical values ​​represent the mass (g) of each component.

[0225] The raw materials used are as follows.

[0226] Specific activators: Ethylamine·HBr, Cyclohexylamine·HBF4

[0227] Other active agents: diphenylguanidine·HBr, dicyclohexylamine·HBF4

[0228] Terpene phenol resin:

[0229] Resin A 200±10mgKOH / g

[0230] Resin B 150±10mgKOH / g

[0231] Resin C 120±10mgKOH / g

[0232] Resin D 100±10mgKOH / g

[0233] Resin E 60±10mgKOH / g

[0234] <Evaluation>

[0235] 《Evaluation of the solubility of active agents》

[0236] Add the activator to resins A to E to prepare a mixed solution. Heat the mixed solution to a temperature above the softening point of the resin and then cool it to room temperature. Check whether there is precipitate in the mixed solution during heating and after cooling, and evaluate based on the following criteria. The results are shown in Tables 1 to 6.

[0237] Judgment criteria:

[0238] A: The activator was dissolved in the mixed solution by heating, and no precipitate was observed after cooling.

[0239] B: The activator did not dissolve in the mixed solution even when heated, and precipitates were observed after cooling.

[0240] [Table 1]

[0241] Test Example 1 Test Example 2 Test Example 3 Test Example 4 Test Example 5 Ethylamine·HBr 0.1 0.1 0.1 0.1 0.1 <![CDATA[Cyclohexylamine·HBF4]]> Diphenylguanidine HBr <![CDATA[Dicyclohexylamine·HBF4]]> Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A B B B B

[0242] As shown in Table 1, in Test Example 1 containing ethylamine·HBr and resin A, no precipitate was observed after cooling.

[0243] On the other hand, in Test Examples 2 to 5 containing ethylamine·HBr and any one of Resins B to E, ethylamine·HBr did not dissolve in the mixed solution even when heated.

[0244] [Table 2]

[0245] Test Example 6 Test Example 7 Test Example 8 Test Example 9 Test Example 10 Ethylamine·HBr <![CDATA[Cyclohexylamine·HBF4]]> 0.1 0.1 0.1 0.1 0.1 Diphenylguanidine HBr <![CDATA[Dicyclohexylamine·HBF5]]> Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A A B B B

[0246] As shown in Table 2, in Test Examples 6 and 7 containing cyclohexylamine·HBF4 and Resin A or Resin B, no precipitate was observed after cooling.

[0247] On the other hand, in Test Examples 8 to 10 containing cyclohexylamine·HBF4 and any one of Resins C to E, cyclohexylamine·HBF4 did not dissolve in the mixed solution even when heated.

[0248] [Table 3]

[0249] Test Example 11 Test Example 12 Test Example 13 Test Example 14 Test Example 15 Ethylamine·HBr <![CDATA[Cyclohexylamine·HBF4]]> Diphenylguanidine HBr 0.1 0.1 0.1 0.1 0.1 <![CDATA[Dicyclohexylamine·HBF4]]> Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A A A A B

[0250] As shown in Table 3, in Test Examples 11 to 14 containing diphenylguanidine·HBr and any of Resins A to D, no precipitate was observed after cooling.

[0251] On the other hand, in Test Example 15 containing diphenylguanidine·HBr and Resin E, diphenylguanidine·HBr did not dissolve in the mixed solution even when heated.

[0252] [Table 4]

[0253] Test Example 16 Test Example 17 Test Example 18 Test Example 19 Test Example 20 Ethylamine·HBr <![CDATA[Cyclohexylamine·HBF4]]> Diphenylguanidine HBr <![CDATA[Dicyclohexylamine·HBF4]]> 0.1 0.1 0.1 0.1 0.1 Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A A A A A

[0254] As shown in Table 4, in Test Examples 16 to 20 containing dicyclohexylamine·HBF4 and any one of Resins A to E, no precipitate was observed after cooling.

[0255] [Table 5]

[0256] Test Example 21 Test Example 22 Test Example 23 Test Example 24 Test Example 25 Ethylamine·HBr 0.1 0.1 0.1 0.1 0.1 <![CDATA[Cyclohexylamine·HBF4]]> 0.1 0.1 0.1 0.1 0.1 Diphenylguanidine HBr <![CDATA[Dicyclohexylamine·HBF4]]> Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A A B B B

[0257] As shown in Table 5, in Test Examples 21 and 22 containing ethylamine·HBr and cyclohexylamine·HBF4 and any of Resins A and B, no precipitate was observed after cooling.

[0258] On the other hand, in Test Examples 23 to 25 containing ethylamine.HBr, cyclohexylamine.HBF4 and any one of Resins C to E, ethylamine.HBr and cyclohexylamine.HBF4 did not dissolve in the mixed solution even when heated.

[0259] [Table 6]

[0260] Test Example 26 Test Example 27 Test Example 28 Test Example 29 Test Example 30 Ethylamine·HBr <![CDATA[Cyclohexylamine·HBF4]]> Diphenylguanidine HBr 0.1 0.1 0.1 0.1 0.1 <![CDATA[Dicyclohexylamine·HBF4]]> 0.1 0.1 0.1 0.1 0.1 Resin A (200±10mgKOH / g) 1.9 Resin B (150±10mgKOH / g) 1.9 Resin C (120±10mgKOH / g) 1.9 Resin D (100±10mgKOH / g) 1.9 Resin E (60±10mgKOH / g) 1.9 Evaluation of the solubility of active agents A A A A B

[0261] As shown in Table 6, in Test Examples 26 to 29 containing diphenylguanidine.HBr and dicyclohexylamine.HBF4 and any of Resins A to D, no precipitate was observed after cooling.

[0262] On the other hand, in Test Example 30 containing diphenylguanidine.HBr, dicyclohexylamine.HBF4, and any one of Resins C to E, diphenylguanidine.HBr and dicyclohexylamine.HBF4 were not dissolved in the mixed solution even when heated.

[0263] From the above results, it is understood that the halogenated salt of the primary amine is dissolved by selecting a terpene-phenol resin having a hydroxyl value exceeding 130 mgKOH / g.

[0264] In addition, it was found that the halide salt of the primary amine cannot be dissolved in the terpene-phenol resin having a hydroxyl value of 130 mgKOH / g or less.

[0265] <Preparation of flux>

[0266] (Examples 1 to 15, Comparative Examples 1 to 3)

[0267] The fluxes of Examples and Comparative Examples were prepared according to the compositions shown in Tables 7 and 8 below. The compositions in Tables 7 and 8 are in mass % when the total amount of the flux is 100 mass %.

[0268] Specific activators: Ethylamine·HBr, Cyclohexylamine·HBF4

[0269] Other active agents: diphenylguanidine·HBr, dicyclohexylamine·HBF4, succinic acid

[0270] Terpene phenol resin:

[0271] Resin A 200±10mgKOH / g

[0272] Resin B 150±10mgKOH / g

[0273] Resin C 120±10mgKOH / g

[0274] Resin D 100±10mgKOH / g

[0275] Resin E 60±10mgKOH / g

[0276] Rosin: Acrylic acid modified hydrogenated rosin, acrylic acid modified rosin, hydrogenated rosin, polymerized rosin, rosin ester

[0277] Solvent: 2-Propanol

[0278] Other resin components: Silicone resin

[0279] Antioxidants: Quinoline compounds

[0280] <Preparation of molten solder>

[0281] As a mother alloy, an ingot composed of an alloy containing 3 mass % of Ag, 0.5 mass % of Cu, and the balance of Sn was prepared.

[0282] The ingot is melted to prepare molten solder.

[0283] 《Evaluation of surface precipitation of flux residue》

[0284] Verification method:

[0285] By spraying the flux of each example onto the substrate, a pre-treated substrate was obtained.

[0286] Next, flow soldering is performed by bringing molten solder into contact with the pre-treated substrate in a nitrogen atmosphere.

[0287] The presence or absence of precipitation of flux residue on the surface of the substrate was confirmed, and evaluation was performed based on the following criteria. The results are shown in Tables 7 and 8.

[0288] Judgment criteria:

[0289] A: No precipitate was observed on the surface of the flux residue.

[0290] B: A small amount of precipitates was observed on the surface of the flux residue.

[0291] C: A large amount of precipitates were observed on the surface of the flux residue.

[0292] In the evaluation results, the amount of precipitates on the surface of the flux residue increases in the order from A to C. The fluxes with evaluation results A to B are acceptable, and the flux with evaluation result C is unacceptable.

[0293] [Table 7]

[0294]

[0295] [Table 8]

[0296]

[0297] The evaluation of the fluxes of Examples 1 to 14 containing the halide salt of a primary amine and the terpene-phenol resin having a hydroxyl value exceeding 130 mgKOH / g was A or B for the precipitation of the flux residue on the surface.

[0298] The soldering flux of Example 15 containing a halogenated salt of a primary amine, an organic acid, and a terpene-phenol resin having a hydroxyl value exceeding 130 mgKOH / g was evaluated as B in terms of precipitation of the soldering flux residue on the surface.

[0299] On the other hand, the fluxes of Comparative Examples 1 to 3 containing a halide salt of a primary amine and a terpene-phenol resin having a hydroxyl value of 130 mgKOH / g or less were evaluated as C for precipitation of flux residue on the surface.

[0300] Industrial Applicability

[0301] According to the present invention, a flux and a method for producing a joint body can be provided that can further suppress the precipitation of an activator in the flux residue after soldering. The flux can be used for flow soldering and soldering of electronic substrates used in a high temperature and high humidity environment.

Claims

1. A soldering flux comprising rosin, terpene phenol resin and an activator, The terpene phenol resin has a hydroxyl value exceeding 130 mgKOH / g, The active agent comprises a halide salt of a primary amine.

2. The soldering flux according to claim 1, wherein The halide salt of the primary amine is a compound represented by the following general formula (1): R 1 -NH2·R 2 ···(1) In the formula, R 1 represents a hydrocarbon group which may have a substituent; R 2 represents HX, BX3 or HBX4; X represents a halogen atom.

3. The soldering flux according to claim 1, wherein The content of the terpene phenol resin is 0.1% by mass or more and 10% by mass or less relative to the total mass (100% by mass) of the soldering flux.

4. The soldering flux according to claim 2, wherein: The content of the terpene phenol resin is 0.1% by mass or more and 10% by mass or less relative to the total mass (100% by mass) of the soldering flux.

5. The soldering flux according to any one of claims 1 to 4, wherein The content of the halide salt of the primary amine is 0.01% by mass or more and 5% by mass or less relative to the total mass (100% by mass) of the soldering flux.

6. The soldering flux according to any one of claims 1 to 4, wherein The ratio (mass ratio) of the content of the halide salt of the primary amine relative to the content (100 parts by mass) of the terpene-phenol resin is greater than or equal to (5 parts by mass) and less than or equal to (150 parts by mass).

7. The soldering flux according to claim 5, wherein The ratio (mass ratio) of the content of the halide salt of the primary amine relative to the content (100 parts by mass) of the terpene-phenol resin is greater than or equal to (5 parts by mass) and less than or equal to (150 parts by mass).

8. The soldering flux according to any one of claims 1 to 4, wherein The soldering flux further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

9. The soldering flux according to claim 5, wherein: The soldering flux further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

10. The soldering flux according to claim 6, wherein The soldering flux further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

11. The soldering flux according to claim 7, wherein The soldering flux further contains an organic acid having a solubility parameter (SP value) of 11.00 or more.

12. A method for preparing a conjugate, comprising: A process for obtaining a joint body by soldering a solder alloy on the surface of a substrate treated with the flux according to any one of claims 1 to 11.

Images